CN106324032A - Calorimetric bionic competitive detection method for detecting pesticide Atrazine residue - Google Patents
Calorimetric bionic competitive detection method for detecting pesticide Atrazine residue Download PDFInfo
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Abstract
The invention relates to a calorimetric bionic competitive detection method for detecting pesticide Atrazine residue, and belongs to the field of biosensors. The method is used for rapid detection of pesticide Atrazine residue in foodstuff or water source samples, and S-MIP is used as an identification element and filled in a reaction column. A competitive binding is carried out between a sample to be measured which is treated by simple pretreatment and a certain amount of beta-lactamase labeled objects to be detected in a mobile phase on blotting sites on S-MIP. Thermal signals released by adding a substrate with enzyme specificity and content of the objects to be detected are in inverse ratio. A standard curve is established based on an optimal experiment condition. The calorimetric bionic sensing method for quantitative detection of the typical pesticide Atrazine with a specific 'amplification method' has the advantages of simple pre-treatment, high sensitivity, good specificity, and quantitative detection.
Description
Technical field
The present invention relates to a kind of bionical race detection method of calorimetric detecting atrazine residual, belong to field of biosensors, for quickly inspection
Survey the atrazine residual in food or water source sample, have that sample pre-treatments is easy, highly sensitive, the advantage of high specificity, detection by quantitative.
Background technology
Herbicide atrazine (Atrazine, ATR) has another name called atrazine, and full name is 2-chloro-4-ethamine-6-2-aminopropane .-1,3,5-triazines, and molecular weight is 215.69
Triazine herbicide as before selectivity inner sucting conduction type Seedling, herbicide after seedling, reached the purpose cut weeds by inhibited photosynthesis, from previous generation
Record and obtained large area use since Development and Production the fifties, be mainly used in the dry lands such as Semen Maydis, Sorghum vulgare Pers., Caulis Sacchari sinensis, fruit tree, forest land, wherein with Aunar
Draw Tianjin (ATR) most widely used；ATR has certain residual toxicity, can suppress the photosynthesis of multiple algae in water body, makes the physiology merit of fish
Can get muddled, kill water-bed arthropod, the chromosome that can cause mice time serious is impaired.Under low concentration exposes for a long time, ATR can make human body
Hormonal system and reproductive system disorderly, there is potential carcinogenesis.In consideration of it, ATR residue limits in water body is made that bright by many countries
Really regulation: Environmental Protection Agency USA specifies that ATR maximum permissible concentration in water is 3 μ g/L, and in European Union's regulation drinking water, ATR content must not exceed
0.1 μ g/L, national environmental protection portion of China specifies that in surface water (1-2 class), the maximum permissible concentration of ATR is 3 μ g/L.The environment that ATR residual causes is dirty
Dye and health hazard problem have caused the extensive concern of people.Therefore, in the urgent need to setting up the method for quick of ATR residual in practical work.
The common method realizing accurately analyzing to ATR has GC-MS, HPLC-MS and sensor detection etc..These detection methods are mainly by right
The change of the optical, electrical signal of sample realizes detection, thus sample pre-treatments requires height, and program is loaded down with trivial details, and elapsed time is long, and instrument sets
For costliness, need professional operator, significantly limit the foundation of method for quick.Immunological detection method have method quickly, easy,
The advantages such as sensitive height, high specificity, portable devices, make it suitable for quickly detect, have good effect when the sample that detection matrix components is single,
But when complex matrices sample, detection signal is subjected to matrix optical characteristic severe jamming, it addition, apply during pesticide residue enrichment method
Organic solvent the activity decrease of antibody can be made even to lose, the immunoreation of follow-up antigen-antibody can be disturbed, strongly limit immunological method quick
Detect the application of little molecule residual.
Calorimetric sensors is to detect heat absorption adjoint in biological respinse or heat production signal.One of its general character is through immobilized enzyme to specificity
The change of heat content in the catalytic reaction of substrate and realize detection.This detection technique has good versatility and detection stability.Method is analyzed with other
Compare and there is many advantages, such as: most of biological samples can be analyzed, immobilized enzyme is reusable, detection not by optical, electrical of sample
The interference of environmental characteristics, the lower detection mutually that can realize flowing continuously, detection process is easy, can introduce reference parts etc..Due to heat sensing element without
The most directly contact with flowing, thus eliminate sensor drift phenomenon.Calorimetric sensors is used at first to glucose and the detection of carbamide, the most gradually
It is applied to the fields such as clinical medicine, environmental monitoring, food hygiene, Industrial Process Monitoring.Due to the thermal discharge that detection thermal signal reaction is total, thus inspection
Survey and lack the deficiency that specificity is such detection method.For not mated, on pH and ionic strength, the non-specific signals caused by carrier fluid and sample
Response can be by carrying out signal difference opposite sex detection overcome diluted sample or introducing reference column.In calorimetric detection method, thermal signal is with the form at peak
Occurring, it is linear with concentration of substrate that peak height is proportional to thermal discharge, peak area and the peak rate of rise.Calorimetric biological detection (TELISA) is base
In the method that MBP enzyme linked immuno-adsorbent assay ultimate principle combines calorimeter detection thermal signal.It is a kind of simple that Scheper et al. utilizes sandwich assay to establish
TELISA method is in order to detect various IgG.It is a kind of in quickly detection corn straw that Qie Zhiwei etc. utilize direct competition method principle to establish first
The TELISA method of typical case's triazine-G-30027 residual, is successfully realized the calorimetry detection to pesticide residues.Wherein, calorimetric sensing
The surface imprinted material that in device reaction column, solid phase carrier is filled successively employs the materials such as CPG microsphere, Protein G, achieves preferable effect.
Molecular engram material contains the molecularly imprinted polymer (MIP in abundant traces holeS) be synthetic receptor, it have similar natural antibody or
The specificity of enzyme and selectivity, this biomimetic sensor containing synthesis recognition component can use in various rugged environments.MIPSComprise a large amount of
Trace hole, these holes can carry out complementation by shape, size and functional group's (such as hydrogen bond) with target molecule, and it is particularly well-suited to little molecule
Detection.
Summary of the invention
First purpose of the present invention is to provide the surface imprinted material that solid phase carrier in a kind of calorimetric sensors reaction column is filled, and it is characterized in that passing through
The specificity for G-30027 that controlled perforated glass pearl (CPG) that surface imprinted technology (s-MIT) is modified in amination is surface imprinted prints
Trace layer product (s-MIP).
Second object of the present invention is to provide a kind of calorimetric bionical race detection method method detecting atrazine residual.
Technical scheme is summarized as follows:
S-MIP is filled in reaction column as recognition component by the present invention.By testing sample after simple pre-treatment flowing mutually lower with a certain amount of β-
Imprinted sites on the determinand competition binding S-MIP of lactamase marker.The thermal signal of addition enzyme spcificity substrate release and determinand content are in instead
Ratio.Criterion curve on the basis of optimization experiment condition, finally sets up that sample pre-treatments is easy, " amplifying method " special, detection by quantitative allusion quotation
The bionical method for sensing of calorimetric of type atrazine, specifically comprises the following steps that
The preparation of 1.S-MIP
(1) 2.85g G-30027 is dissolved in 100ml DMF (DMF) acetate buffer mixed solution (DMF: acetate buffer=9: 1,
v/v；Acetate buffer, 0.2mol/L, pH5.8).It is made to be completely dissolved under conditions of mechanical agitation；
(2) there is free bead (CPG) by controlled to 5.635ml methacrylic acid (MAA), 1.46g methylene-bisacrylamide (BIS) and 400mg successively
Add in the mixed solution of step (1), form trace prepolymerization system；
(3) 38 DEG C of water-baths, system prepolymerization 12h under the conditions of stirrer rotating speed 300rpm；
(4) prepolymerization system is passed through nitrogen 30min, adds the polymerization of Ammonium persulfate. (APS) initiation grafting trace, reacts 10h；
(5) trace product is separated from system by vacuum filtration through sand core funnel；
(6) use 50% methanol aqueous solution, pH 8～9, under the conditions of the regenerated liquid containing 1mol/L NaCl 37 DEG C, product regeneration 24h, period every 8h are updated
Regenerated liquid 1 time.In vacuum drying oven dry for standby after the product alcohol flushing prepared.Products therefrom is scanned Electronic Speculum simultaneously characterize
(SEM) identifying, result is as shown in Figure 1.From SEM phenogram, CPG surface forms obvious imprinted layer.
In method, function monomer methacrylic acid (MAA) and cross-linking agent methylene-bisacrylamide (BIS) mol ratio are 7: 1；Function monomer is p-
Sodium styrene sulfonate (SSS) and template molecule G-30027 (ATR) mol ratio are 5: 1
2.MIP calorimetry detection G-30027: MIP measures heat detecting device as shown in Figure 2:
(1) surface imprinted product loading reactor is placed in heat regulator, is passed through and filters and the carrier fluid (0.02 of ultrasonic degasification through 0.22 μm pin type filter
mol L-1, the acetic acid-sodium acetate buffer solution of pH 5.8, containing 2%DMF) and equiulbrium flow kinety system, system flow velocity 1000 μ lmin-1；
(2) with carrier fluid be solvent prepare 0-20ng mL-1The G-30027 solution of gradient concentration, mixes with the G-30027 of a certain amount of beta-lactam enzyme labelling
Conjunction is prepared as sample.
(3) after 0.22 μm pin type filter filters, sample solution is added.Determinand descends competition binding S-MIP surface with enzyme mark determinand mutually in flowing
Trace hole.Unnecessary sample flushes out reaction column mutually with flowing.
(4) add thermal signal change produced by specific substrate ampicillin collected by Wheatstone bridge, convert after at calorimetric work station (N2000
Data Processing in Chromatography Workstation) on show with peak-to-peak signal；
(5) can complete in 10min completely to the generation of enzymatic reaction thermal signal from addition sample, add baseline restorer after background signal value detection, regeneration,
One sample complete detection time is less than 30min.Cleaning Principle is as shown in Figure 3:
3. the foundation of calorimetry detection G-30027 method
The optimization of 3.1 experiment conditions
This experiment is selected surface imprinted material as solid phase carrier and recognition component, be because: 1, permeability most commonly used in calorimetric method is solid
Phase support C PG surface carries out trace and is beneficial to control particle diameter and the pore size control of trace product, makes trace product not produce the highest background under flowing mutually
Pressure；2, carry out the surface imprinted mechanical stability that may insure that imprinted material on CPG microsphere, improve the dry of trace product tolerance flowing opposed configuration
The ability disturbed；3, the preparation of permeability microsphere upper surface imprinted material is beneficial to the rapid identification of quality transmission, beneficially trace hole and target molecule, profit
Foundation in calorimetric method；
Carrier fluid flow velocity not only determines to detect flux, and in affecting the unit interval, thermal signal produces intensity and signal stabilization simultaneously.Along with the lifting of flow velocity,
Same sample signal response intensity is gradually increasing.It is 1000 μ l min to flow velocity-1Time signal the strongest.According to experimental observation, flow velocity continues to raise very
Flowing shakiness and leakage mutually easily occur, thus selectes 1000 μ l min-1For Optimal system flow velocity.In detection system temperature under same operation mode
25, carry out same sample signal measuring at 30,37 DEG C, observe that signal signal under the conditions of 30 DEG C is the strongest, and regeneration effect is best, thus choosing
Fixed 30 DEG C is detection system temperature.
0.02molL selected by carrier fluid-1The acetic acid-sodium acetate buffer solution of pH 5.8.Optimize wherein additive DMF content, rise to 8% from 2%.
Observing that when DMF is 4%, Competitive assays amplitude is obviously reduced, when being 8%, Competitive assays phenomenon disappears.But it must be ensured that the dissolving enough to ATZ
Degree.Therefore selecting DMF content is 2%.Containing ATZ-β (the 0.8mg ml according to 1: 100 dilution-1) sample add after along with substrate add time
The increase of number, signal intensity has the trend gradually risen, and under the conditions of pointing out this, ATZ-β may excess.Under the conditions of Gai, the ATZ-β of rather high concentration
Existential Space steric hindrance, enzyme spcificity substrate catalytic reaction is carried out by impact.Thus ATZ-β is carried out gradient dilution, make according to signal response optimization
Use thinner ratio.
Found that 1: 200 compared with 1: 400 group of signal 1: 100 group of signal intensity slightly reduce, but when 1: 800, signal is remarkably decreased, and carries
Show that now ATZ-β can not fully combine trace hole, thus selecting 1: 400 group is optimal thinner ratio.Carry out the optimization of regeneration condition with this understanding,
Find 1000 μ l min-1Under the conditions of 1molL-1The 50% methanol aqueous solution regeneration 2min of NaCl can obtain satisfied regeneration effect.At this
Calorimetric signal is measured on the basis of optimization.Repeat after loading to add substrate, present very fast decline along with substrate adds the increase signal intensity of indegree, say
Bright ATZ-β concentration is to optium concentration.As shown in Figure 4.Can also be observed that simultaneously, produce completely to enzymatic reaction thermal signal from adding sample
Can complete in 10min, add baseline restorer after background signal value detection, regeneration, sample complete detection time is less than 30min.
On the basis of ATZ-β dilutes, optimize substrate concentration further.In Fig. 5 visible, Amp concentration 1,2,4mmol L-1 liter
Time high, signal intensity is multiplied.At 6mmol L-1Time signal increasing degree be remarkably decreased, illustrate that this concentration is close to saturated catalytic level.Thus Amp
4mmol L-1Being considered the concentration most sensitive to Enzyme activities, this concentration selected carries out method foundation.
3.2 detection method standard curve is set up
On the basis of experimental condition optimization, draw standard curve (see Fig. 6).Data point repeats for equal 3 times.
It is computed this Competitive assays curve linear detection range (IC20-IC80) it is 0.6-4.1ng ml-1, detection limit IC10For 0.4ng ml-1。
3.3 detection method specificitys
The Simanex similar with ATR structure, tripolycyanamide, the specificity of phloroglucinol assay method are selected.Three is at low concentration (5 μ g L-1)
All do not observe Competitive assays phenomenon, until concentration brings up to 50 μ g L-1.ATZ is equivalent to by calculating the Competitive assays signal produced under this concentration
Produce identical Competitive assays intensity concentration proportion calculate cross reactivity.The triazine herbicide cross reactivity that S-MIP is similar to structure height
It is only 5.7%, illustrates that imprinting effect is fine.It is 3.7% to tripolycyanamide cross reactivity, may be tripolycyanamide nitrogen-atoms proton and trace hole
There is electrostatic adsorption, form a certain degree of identification.Phloroglucinol does not observes cross reactivity, and the trace hole height for space conformation is described
Degree selectivity.The above analysis understands, and this trace hole has good identification ability.
3.4 recovery testu
ATR recovery testu and methodology comparison result (n=3) in table 1 tap water
1 mean；2 standard deviations
Owing to this method detection sensitivity is ng ml-1Level, thus selected UPLC-MS/MS carries out methodology comparison.Experimental result is shown in Table 1.
From in table, have with UPLC-MS/MS based on the S-MIP bionical detection method of competition law calorimetric set up that combines with calorimetric sensing detection technology
There is preferable comparability.Also achieve the flowing with S-MIP as recognition component herein and descend the foundation of calorimetric detection technique mutually.The preparation that MIP is possessed
Simplicity, identification specificity are strong and environmental stability is easy with the sample pre-treatments of calorimetric sensing technology, be easily achieved continuous and automatic detection combines,
Achieve the quick specific detection to pesticide residues first.
Simultaneously as the method recognition component has certain versatility at preparation principle, and method can to realize the high specific to object quick
Detection, can complete the detection of a sample in 30min, be extremely suitable for promoting in practice.The method is as the sample of detection pesticide residues
Pre-treatment specific detection method easy, quick, has a good application prospect.
Accompanying drawing explanation
Through SEM phenogram, (left figure is CPG bare ball to Fig. 1 S-MIP；Right figure is S-MIP)
Fig. 2 MIP based on competition law calorimetric bionical detection device schematic diagram
Fig. 3 MIP based on competition law calorimetric bionical Cleaning Principle schematic diagram
Before Fig. 4 ATZ-β concentration optimization, 1. the contrast of (upper figure) (figure below) calorimetric signal afterwards is background signal peak；The most 4. for catalysis signal peak
Concentration of substrate optimization under the conditions of Fig. 5 ATZ-β 1: 400
Fig. 6 calorimetric bionical detection method detection ATZ standard curve
Detailed description of the invention
Below example facilitates a better understanding of the present invention, but does not limit the present invention.Experimental technique in following embodiment, if no special instructions,
It is conventional method.Reagent used in following embodiment and material, if no special instructions, all can be commercially available from conventional reagent company.
Technical scheme: the preparation method of a kind of diethylstilbestrol cation complete antigen:
Embodiment 1
S-MIP is prepared according to step 1.
(1) surface imprinted product loading reactor is placed in heat regulator, is passed through and filters and the carrier fluid (0.02 of ultrasonic degasification through 0.22 μm pin type filter
mol L-1, the acetic acid-sodium acetate buffer solution of pH 5.8, containing 2%DMF) and equiulbrium flow kinety system, system flow velocity 1000 μ l min-1；
(2) with the G-30027 solution that carrier fluid is solvent preparation 0-20ng mL-1 gradient concentration, with the G-30027 of a certain amount of beta-lactam enzyme labelling
It is prepared by mixing into sample.
(3) after 0.22 μm pin type filter filters, sample solution is added.Determinand descends competition binding S-MIP surface with enzyme mark determinand mutually in flowing
Trace hole.Unnecessary sample flushes out reaction column mutually with flowing.
(4) add thermal signal change produced by specific substrate-ampicillin collected by Wheatstone bridge, convert after at calorimetric work station (N2000 color
Modal data work station) on show with peak-to-peak signal；
(5) can complete in 10min completely to the generation of enzymatic reaction thermal signal from addition sample, add baseline restorer after background signal value detection, regeneration,
One sample complete detection time is less than 30min.
Claims (2)
1. detecting the bionical race detection method of calorimetric of atrazine residual, in it is characterized in that calorimetric sensors reaction column, solid phase carrier is filled
Surface imprinted material be the controlled perforated glass pearl modified in amination by the surface imprinted technology with methacrylic acid as function monomer
(CPG) surface imprinted specificity imprinted layer product (s-MIP) for G-30027.
2. detect the bionical race detection method of calorimetric of atrazine residual, it is characterized in that carrier fluid uses 0.02mol L-1The acetic acid of pH 5.8
-sodium acetate buffer its additive DMF content is 8%.Regeneration condition is 1mol L-1The 50% methanol aqueous solution regeneration 2min of NaCl,
Linear detection range (IC20-IC80) it is 0.6-4.1ng ml-1, detection limit IC10For 0.4ng ml-1。
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Cited By (1)
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| CN110132927A (en) * | 2019-06-10 | 2019-08-16 | 中国农业科学院农业质量标准与检测技术研究所 | Inhibit the pesticide residue fluorescence detection method of principle based on molecular engram bionic enzyme |
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| CN102417558A (en) * | 2011-11-21 | 2012-04-18 | 嘉兴学院 | Magnetic molecularly imprinted polymer for separating atrazine, and preparation method for magnetic molecularly imprinted polymer |
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| CN102417558A (en) * | 2011-11-21 | 2012-04-18 | 嘉兴学院 | Magnetic molecularly imprinted polymer for separating atrazine, and preparation method for magnetic molecularly imprinted polymer |
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| CN110132927A (en) * | 2019-06-10 | 2019-08-16 | 中国农业科学院农业质量标准与检测技术研究所 | Inhibit the pesticide residue fluorescence detection method of principle based on molecular engram bionic enzyme |
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